Interpolymer formed from monovinylaromatic polymer, drying oil or acid, polyhydric alcohol, and polybasic acid



"polymer of a monovinylaromatic compound, froln (1943), at least as great as that of dehyabout to per cent of a polyhydric alcohol, drated castor oil (a minimum of approximately and at least a portion of a polybasic acid. The 133 and 33 Woburn) and not in excess of that resinous product has a sufflciently low acid value for beta-eleostearic acid (approximatel 274 and to allow employment thereof with reactive pig- 35 91 Woburn). As ordinarily obtained from comments and aminoaldehyde resins. The inter mercial sources, the drying oils consist chiefly of polymer, when in solution in any of the commonglycerides of the drying oil fatty acids, which ly employed varnish or paint solvents, show acids maybe liberated from the oils by saponificasuperior color and clarity, and films formed theretion and acidulation of separated acid salts.

Patented Apr. 24, 1951 r INTERPOLYl /[ER FORMED FROM MONO- VINYLAROMATIC POLYMER, DRYING OIL OR ACID, POLYHYDRIC ALCOHOL, AND POLYBASIC ACID Edward G. Bobalek, Cleveland, Ohio, assignor to The Area Company, Cleveland, Ohio, a corporation of Ohio No Drawing. Application June 2, 1947, Serial No. 751,967

8 Claims. (Cl. 26022) l 2 The present invention relates to a novel type of within the scope of monovinylaromatic comresinous interpolymer, and is more particularly pound may be mentioned styrene itself, paraconcerned with the product formed from the reacmethylstyrene, para-chlorostyrene, para-fluorotion of (a) an at least partially ju ed d ystyrene, meta-chlorostyrene, meta-fluorostyrene,

ing oil fatty acid 'or ester, (b) an oil-soluble polymetaand para-trichloromethylstyrene, metamer of a monovinylaromatic compound, (0) a and. para-trifluoromethylstyrene, orthoand polyhydric alcohol, and (d) a polybasic acid. meta-hydroxystyrene, methoxystyrenes, vinyl- The invention is further concerned withamethod naphthalene, and the like. Substituents may for the production of the said interpolymer, and also be present on the vinyl group, as in alphato surface-coatings embodying the said polyi9 methylstyrene, but of course not in a manner merization product. such as to retard polymerization. Especially pre- It has previously been proposed to incorporate ferred monovinylaromatic compounds are stystyrene into a surface-coating according to varirene itself and derivatives thereof.

ous procedures. Such methods have, for ex- The at least partially conjugated drying oil ample, included the polymerization of styrene in 15 fatty acid or ester may be any one of the at least the presence of a drying oil, a resin, or a cellulosic partially conjugated drying oils, which usually film-forming material (U. S. Patent 1,975,959). exist chiefly as the glycerides of certain complex Other methods of incorporating styrene into a unsaturated straight-chain organic acids, the oil surface-coating have likewise been suggested, fatty acids themselves, or synthetic esters of the and products produced therefrom have exhibited, drying oil fatty acids. The conjugated drying in certain instances, at least some improvement oil or acid, to be operative in the method of the over the ordinarily employed types of surfacepresent invention, should have an average double coatings. However, it has not previously been bond content and degree of conjugation, as desuggested to prepare an interpolymer such as that termined by average iodine number and diene of the instant application. 25 number, the former being the experimental meas- The interpolymer of the present invention is ure of unsaturation and the latter being the produced by the interpolymerization of from experimental measure of conjugated unsaturaabout 40 to 60 per cent by weight of an at least tion, according to specifications published by J. D. partially conjugated drying oil fatty acid or ester, von Mikusch and Charles Frazier, Ind. Eng. from 5 to 15 per cent by weight of an oil-soluble Chem. Anal. Ed. 13, 782-789 (1941); 15, 109-113 from exhibit excellent waterand alkali-resist- The oil acids thus obtained may, if desired, be ance as compared with ordinary oil-modified esterified with monohydric or polyhydric alcoy yl p a e T651115- The es n lends r a hols according to usual esteriflcation procedures. durability to paints and varnishes embody ng th These esters are usually referred to as synthetic mae p lyi the an p i f m i drying oil esters, and are similar to the natural nance of adhesion and resistance to checking oil in many respects. Ordinarily, these natural under condltions of atmospheric exposure. fatty acid glyceride esters, the natural drying oil BY i y a ic fcompound as emfatty acids, or various synthetic esters of the mov m the present speclfieatloln 1s m nt y same, are processed by commercial suppliers accompound containing at least a phenyl or naphcording to various procedures which effect an thyl radical 1n combination with a vinyl group, 59 average double bond content and. degree of conand otherwise structurally similar to styrene. jugation such as t render the processed oils or The D l up may contain substituents as, acids suitable for employment in the present infor example, fluorine, chlorine, methoxy, hyvention. Either the oil, the acid, or synthetic droxy, methyl, trichloromethyl, or trifluoroesters may be employed in the method of the methyl. As representative. compounds included .5 3 present invention. Mixtures of drying, oils, or

of oils with acids, may also be employed, but, whether in the pure or mixed state, the requirement for conjugation remains the same. Drying oils and acids having a greater or lesser average double bond content than that prescribed above are unsuited for use, and, if the necessary conjugation is not present in the oil or acid as introduced into the reaction zone, then heating or other reaction conditions must be sufiicient to produce the same therein. As representative drying oils and acids which may be employed, for example, are dehydrated castor oil, conjugated linseed oil fatty acids, isomerized walnut oil, conjugated soya oil, tung oil, and blends of these highly conjugated oils and acids with oils such as soya and linseed.

The specifications of a typical oil fatty acid which may be advantageously employed in the preparation of the resin of the present invention are as follows:

1. Iodine No. 143-153 (WIJS) 178-187 (Woburn) 2. Color 1-2' 3. Acid No. 197.5 to 199 4. Saponification No 198.5 to 199.5 5. Ester value -1.5 6.. Hexabromide value 0-3 7. WIJS on ice for 3 min- 115-120 (62-73 utes Iodine value. Woburn) 8. Conjugation (by dif- 60-65 ference). 9. Titre value 18-24 10. Spec. gravity 0.9201 at 25 C. 11. Viscosity A+ to F (Gardner- Holdt scale at 77 F.)

By a polyhydric alcohol, as employed herein, is intended any polyhydric alcohol containing at least three hydroxyl groups in the molecule, for example, glycerol, pentaerythritol, polyallyl alcohol, mannitol, sorbitol, erythritol, trimethylol propane, and similar other alcohols containing at least three hydroxyl groups. The amount of polyhydric alcohol employed is usually between about 15 to 25 per cent of the total weight of starting reactants, and is always in excess of that amount theoretically required to neutralize all carboxyl groups in the starting reactants.

As polybasic acid in the present invention may be employed any polybasic acid or the anhydride thereof, such as the dibasic acids malonic, suc cinic, glutaric, adipic, sebacic, maleic, itaconic, methylmalonic, perfluoroglutaric, perfiuoroadipic, and phthalic; tribasic acids such as 1,2,4-butanetricarboxylic acid, and the like. At least a portion of a polybasic acid must always be added, and, for the production of the most desirable product, suilicient of the polybasic acid should be added to render the ratio of hydroxyl groups to carboxyl groups in the starting reactants between about 1.1 and 2.0 to 1, preferably between about 1.1 and 1.6 to 1. This ratio allows the polybasic acid to react with the required excess of polyhydric alcohol, efiecting considerable of the highly desirable cross linkage.

The principle of the present invention is not restricted to the employment of any particular oil-soluble monovinylaromatic compound, but rather contemplates the use of any oil-soluble polymer of a monovinylaromatic compound in amount between about 5 and per cent by weight of the starting reactants. Such a polymer is ordinarily of a rather low average molecular weight, but as long as the polymer, which usually @8313 as a mixture of polymers of varying molecular weights, be oil-soluble, the exact molecular weight is of little significance. A satisfactory test of a particular monovinylaromatic polymer, to determine its suitability for employment, is to admix 15 parts thereof with parts of dehydrated castor oil and to heat the mixture at an elevated temperature. This amount of polymer should go into solution in the oil at elevated temperatures and should not separate out upon cooling. Other entirely satisfactory tests may be devised, and to state that the monovinylaroinatic polymer should be oil-soluble should suffioe to inform one skilled in the art. It is to be understood, also, that the oil-soluble polymer of the monovinylaromatic compound need not be of an entirely pure nature, as mixtures of oil soluble monovinylaromatic polymers may be employed successfully, as well as oil-soluble polymers of a monovinylaromatic compound containing minor proportions of modifying resins, or chemical inhibitor agents which limit the molecular weight of the monovinylaromatic compound polymer. These modifying resins and inhibitors should ordinarily not exceed about 15 per cent of the weight of the monovinylaromatic polymer. Representative polymers which have been found especially suitable are oil-soluble polystyrenes, oil-soluble phenolicmodified polystyrenes, oil-soluble poly(alphamethyl) styrenes having an average molecular weight between about 350 and 800, mixtures of the foregoing, phenolic modified poly(alphamethyl) styrenes, and the like. Others which may be employed are modified or unmodified oil-soluble polymers of any of the previously mentioned monovinylaromatic compounds. Some of these polymers are available commercially, while others can be prepared by polymerization of the desired monomer by conventional procedure to any extent within the prescribed range of oil-solubility,

In carrying out the method of the present invention, (1) from about 40 to 60 per cent by weight of an at least partially conjugated drying oil fatty acid or ester, (2) from about 5 to about 15 per cent by weight of an oil-soluble polymer of a monovinylaromatic compound, (3) a polyhydric alcohol in excess of that amount theoretically required to neutralize all carboxyl groups in the starting reactants, and (4) a polybasic acid, may be heated together at a resinforming temperature until attainment of an acid value below about 30, preferably below about 10. The reaction may be continued to any desired extent, but should always be checked short of the point at which the reaction product undergoes gelation. The reactants are usually heated together in admixture at a temperature between about 190 and 260 degrees centigrade, preferably between about 200 and 250 degrees centigrade, and in the presence of an esterification catalyst such as litharge or calcium stearate. When carried out in the temperature range given above, the reaction usually demands a period be-' tween about three and six hours, and suitable resin-forming temperatures higher or lower than the above correspondingly afiect the time required. A convenient manner of checking the reaction short of gelation is by dilution of the resin to a solution of about 50 per cent nonvolatile solids in a solvent such as xylene or a petroleum hydrocarbon fraction having a boiling range between about and 200 degrees centirade.

While the alcohol and polybasic acid may be 76 introduced into the reaction simultaneously or in admixture, certain advantages accruing to the employment of specific procedures when operating with diiierent types of reaction ingredients are somewhat preferable. Therefore, when less than about two-thirds of the oil and/or oil fatty acid portion of the reaction mixture consists of oil fatty acids, it is advantageous to heat the polyhydric alcohol together with the oil reactant, either alone or in the presence of the monovinylaromatic polymer, for a short time before addition of the polybasic acid. However, when the oil and/or acid portion of the reaction mixture consists of more than about two-thirds oil fatty acids, no advantage is gained by employment of such procedure, and the polyhydric alcohol and polybasic acid are usually introduced into the reaction at the same time.

The preliminary heating of drying oil and polyhydric alcohol is usually at a temperature between about 130 and 250 degrees centigrade, usually for a period of between about one-half and one hour, and may be considered complete when one part of the reaction mixture, prior to the addition of polybasic acid, is soluble in two parts of methanol by volume. period of preliminary heating, the polybasic acid may be added directly and the reaction continued at any suitable resin-forming temperature, usually between about 200 and 260 degrees centigrade, in the same manner as when the polyhydric alcohol and polybasic acid are added together, during which reaction period a current of carbon dioxide is passed through the reaction mixture to promote removal of the water of esterification.

When the polyhydric alcohol and polybasic acid are introduced into the reaction at the same time, as is usually the practice when drying oil fatty acids make up at least about two-thirds of the drying oil fatty acid or ester portion of the reaction mixture, the temperature may be maintained at any level within the usual range for the formation of a resin, e. g., 1130-260 degrees centigrade, usually between about 190 and 260 degrees centigrade, until the acid number of the resin is below about 30 and preferably below about 10, but always short of the point at which ,gelation of the resin occurs. This usually demands a time period of about two to six hours when carried out within the range given above, and may be conveniently checked short of gelation by dilution to a solution of about 50 per cent non-volatile solids in asuitable solvent.

The polyhydric alcohol in the starting reaction mixture is always in excess of that amount theoretically required to neutralize all of the carboxyl groups in the starting reactants, and ordinarily comprises from about to per cent by weight of the starting reactants. Whether the polyhydric alcohol and polybasic acid are introduced into the reaction mixture simultaneously or at different times, the relative proportions of these reactants are chosen so that the total number of carboxyl groups in the reaction assumes a ratio betwen about 1.]. and 2.0 to .1, and preferably 1.1 and 1.6 to 1.

If desired, solvents such as toluene, xylene, dipentene, or moderately low-boiling aliphatic hydrocarbons may also be incorporated into the reaction mixture, and the reaction conducted under temperature conditions regulated according to the maximum volume of reflux which can be controlled in the particular apparatus employed. The reaction container, may, for example, be provided with a reflux condenser having a re- Upon the expiration of this ceiver whereby the mixed solvent-water condensate is collected and whereby the separated water may be withdrawn while the solvent is returned to the reaction container at a rate sufficient to replace the quantity removed by distillation. In such operation, carbon dioxide or other inert gas may be used as a protective blanket to inhibit oxidation. The fusion process first given is, however, preferred, inasmuch as the process involving the employment of a solvent is not generally productive of a product having such desirable characteristics as that produced by the fusion method.

The following examples illustrate the method of the present invention, but are not to be construed as limiting.

Example 1 A low molecular weight oil-soluble resin consisting in greater part of drying oil soluble polymeric styrene maybe prepared as follows:

A mixture of 5'70 grams of monomeric styrene and 30 grams of para-phenylphenol formaldehyde resin were introduced into a three-neck, one-liter flask provided with reflux condenser, agitator, and thermometer. The reaction mixture was brought to a temperature of -130 degrees centigrade and maintained at this level until a homogeneous solution was obtained. Heating was then discontinued, and a catalyst comprising a mixture of 0.5 gram of boric acid and 0.5 gram of oxalic acid was added to the styrenephenolic solution. The resulting exothermic reaction was controlled by cooling the flask in a water bath in such a manner as to maintain the reaction temperature always below about 1-45 degrees centigrade. When the exothermic reaction had subsided, the reflux condenser was removed and the viscous reaction product maintained at a temperature of 215 degrees centigrade for a period of about one hour, while the remaining volatile matter was blown from the resin with a current of carbon dioxide. The resin was then poured into a shallow dish to freeze into a pale-colored, brittle, thermoplastic solid. This polystyrene resin was found suitable for employment in the process of the present invention.

Example 2 Sixty grams of the phenolic-modified polystyrene from Example 1 and 200 grams of conjugated linseed oil fatty acids were admixed in a three-neck, one-liter flask provided with an agitator, a thermometer, and a means of blowing carbon dioxide through the reaction mixture, at a temperature of about degrees centigrade. Eighty grams of pentaerythritol, 60 grams of phthalic anhydride, and 0.5 gram of litharge were then added, and the reaction mixture maintained at a temperature between about 235 and 250 degrees centigrade for three hours. The product at this point had an acid value of less than ten, and the reaction was checked by dissolving the resin in xylene to produce a sixty per cent solution of non-volatile solids having a viscosity of E-G on the Gardner-Holdt scale at '77 degrees Fahrenheit.

Films drawn from the resin and baked for one-half hour at 250 degrees Fahrenheit were tough and durable, especially in their maintenance of adhesion and resistance to check-ing under conditions of atmospheric exposure, as well as in their waterand alkali-resistance as compared with common oil-modifled glyceryl phthalate resins. r

Example 3 A mixture of 4050 grams of dehydrated castor oil, 900 grams of oil-soluble poly(alpha-methyl) styrene resin having an average molecular weight between about 400 and 800, 1800 grams of penetaerythritol, and 0.3 gram or" litharge were reacted together for a period of about one hour at about 230 degrees centigrade in a five-gallon aluminum kettle, fitted with mechanical stirrer, air-cooled condenser, and a means of blowing carbon dioxide through the mixture. At the end of this time, when one part of the reaction mixture was soiuble in two parts of methanol, 2250 grams of phthalic anhydride was added and the temperature maintained at 215 degrees centigrade until the acid value was less than ten. The time required to attain the desired acid value was about five hours after the addition of phthalic anhydride, and the reaction was checked at this point by dissolving the resin in an equal weight of xylene to give a 50 per cent solution of non-volatile solids having a viscosity greater than S on the Gardner-Holdt scale at 77 degrees Fahrenheit.

Films prepared from this resin were very similar to those drawn from the resin of Example 1, exhibiting even greater durability and additional toughness.

Example 4 The procedure of Example 2 is repeated, employing instead of the polystyrene a low molecular weight oil-soluble poly(alpha-methyl)sty rene. The product is similar to that obtained from the employment of polystyrene itself and is an excellent paint or varnish base from the standpoint or" toughness, durability, and adhesion of films formed therefrom.

As previously stated, the resinous product of the present invention, when in solution in any commonly employed solvent, shows superior color and clarity, and films drawn therefrom exhibit excellent waterand alkali-resistance as compared with ordinary oil-modified glyceryl phthalate resins. The resin is especially retentive of adhesive qualities and resistant to checking and external exposure when in the form of either paint or varnish films.

Coating compositions prepared from the polymer of the present invention and a number of driers, pigments, and resins are especially suitable for employment as varnishes and baking enamels, inasmuch as films formed therefrom exhibit excellent toughness, durability, and resistanee to alkali, water, and exposure. Driers which may be advantageously incorporated with the interpolymer are metallic naphthenates, such as cobalt, magnese and lead. As pigments that may be used in the said coatings may be men tioned titanium dioxide, zinc oxide and iron blue. Among the resins which may be advantageously employed in combination with the interpolymer of the present invention, an oil-soluble phenolaldehyde resin melamine or urea resin, pentaerythritol esters of rosin, ester gum, and, in general, any other hard varnish resins are frequently desirable in effecting minor modifications of film properties. Such a resin is preferably employed in a minor proportion, e. g., in amount up to about 30 per cent by weight of the mixture.

For the preparation of surface coatings from the interpolymer of the present invention, the resin may be diluted to any desirable extent with a common varnish solvent, mineral spirits and xylene being somewhat preferred. The concentration should usually be between about 50 and 60 percent of non-volatile solids, and films pro duced from such solutions have been found especially desirable. The exact concentration employed is not significant, however, as it has been found that variation of the solids content over a resonable range does not materially affect the superior quality of the films.

Various modifications may be made in the invention without departing from the spirit or scope thereof, and it is to be understood that I limit myself only as defined in the appended claims.

I claim:

1. The product of claim '7, wherein the mono vinylaromatic oil-soluble polymer (b) is polystyrene.

2. The process of claim 8, wherein the monovinylaromatic oil-soluble polymer (b) is polystyrene.

3. The process of claim 8, wherein a drying oil is employed, and wherein the polyhydric alcohol (c) is heated together 11th the drying oil (a) and monovinylaromatic polymer (1)) prior to introduction of monomeric polybasic acid (d) into the reaction mixture.

4. The process of claim 3, wherein the polyhydric alcohol (c), monovinylaromatic polymer (b) and drying oil (a) are heatedtogether at a temperature between 130 and 250 degrees centigrade, and wherein the reaction is maintained at a temperature between 190 and 260 degrees centigrade after the addition of the monomeric polybasic acid ((1).

5. The product of claim '7, wherein the monovinylaromatic oil-soluble polymer (b) is poly- (alpha-methyl) styrene.

6. The process of claim 8, wherein the monovinylaromatic oil-soluble polymer (1)) is poly- (alpha-methyl)styrene. v

7. An ungelled resinous interpolymer formed by polymerization of from 40 to 60 percent by weight of (a) a compound selected from the group consisting of drying oils and dryin oil fatty acids having an average Woburn iodine number between about 133 and 274 and an average Woburn diene number between about 33 and 91, (b) from about 5 to 15 percent by weight of an oil-soluble polymer of a monovinylaromatic compound selected from the group consisting of styrene, vinylnaphthalene, fiuorostyrene, chlorostyrene, methoxystyrene, hydroxystyrene, methylstyrene, trichloromethylstyrene, trifiuoromethylstyrene, and alpha-methylstyrene, said monovinylaromatic polymer consisting of at least percent by weight of polymerized monovinylaromatic compound monomer, the remainder being (0) a polyhydric alcohol containing as sole functional groups at least three and not more than six hydroxyl groups per molecule, and (d) a monomeric polybasic organic acid selected from the group consisting of saturated and unsaturated polybasic acids containin carboxyl groups as sole functional groups, the relative proportions of (c) and (at) being such as to render the ratio of hydroxyl groups to carboxyl groups the starting reactants between about 1.1 and 2.0 to 1, the said interpolymer having an acid value below 8. The process for the preparation of a resinous interpolymer which includes the step of polymerizing, by heating together at a resin-forming temperature between about and 260 degreescentigrade (a) from about 40 to 60 percent by Weight of a compound selected from the group consisting of drying oils and drying oil fatty acids hav-- ing an average Woburn iodine number between about 133 and 2'74 and an average Woburn diene number between about 33 and 91, (b) from about 5 to 15 percent by weight of an oil-soluble polymer of a monovinylaromatic compound selected from the group consisting of styrene, vinylnaphthalene, fluorostyrene, chlorostyrene, methoxystyrene, hydroxystyrene, methylstyrene, trichloromethylstyrene, trifiuoromethylstyrene, and alphamethylstyrene, said monovi-nylaromatic polymer consisting of at least 85 percent by weight of polymerized monovinylaromatic compound monomer, the remainder being (0) a polyhydric alcohol containing as sole functional groups at least three and not more than six hydroxyl groups per molecule, and (d) a monomeric polybasic organic acid selected from the group consisting of saturated and unsaturated polybasic acids containing carboxyl groups as sole functional groups, the

relative proportions of (c) and ((1) being such as to render the ratio of hydroxyl groups to carboxyl groups in the starting reactants between about 1.1 and 2.0 to 1, until the attainment of an acid number less than about 30 in the reaction product.

EDWARD G. BOBALEK.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,457,769 Arvin et a1. Dec. 28, 1948 FGREIGN PATENTS Number Country Date 375,320 Great Britain June 20, 1932 

7. AN UNGELLED RESINOUS INTERPOLYMER FORMED BY POLYMERIZATION OF FROM 40 TO 60 PERCENT BY WEIGHT OF (A) A COMPOUND SELECTED FROM THE GROUP CONSISTING OF DRYING OILS AND DRYING OIL FATTY ACIDS HAVING AN AVERAGE WOBURN IODINE NUMBER BETWEEN ABOUT 133 AND 274 AND AN AVERAGE WOBURN DIENE NUMBER BETWEEN ABOUT 33 AND 91, (B) FROM 5 TO 15 PERCENT BY WEIGHT OF AN OIL-SOLUBLE POLYMER OF A MONOVINYLAROMATIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF STYRENE, VINYLNAPHTHALENE, FLUOROSTYRENE, CHLOROSTYRENE, METHOXYSTYRENE, HYDROXYSTYRENE, METHYLSTYRENE, TRICHLOROMETHYLSTYRENE, TRIFLUOROMETHYLSTYRENE, AND ALPHA-METHYLSTYRENE, SAID MONOVINYLAROMATIC POLYMER CONSISTING OF AT LEAST 85 PERCENT BY WEIGHT OF POLYMERIZED MONOVINYLAROMATIC COMPOUND MONOMER, THE REMAINDER BEING (C) A POLYHYDRIC ALCOHOL CONTAINING AS SOLE FUNCTIONAL GROUPS AT LEAST THREE AND NOT MORE THAN SIX HYDROXYL GROUPS PER MOLECULE, AND (D) A MONOMERIC POLYBASIC ORGANIC ACID SELECTED FROM THE GROUP CONSISTING OF SATURATED AND UNSATURATED POLYBASIC ACIDS CONTAINING CARBOXYL GROUPS AS SOLE FUNCTIONAL GROUPS, THE RELATIVE PROPORTIONS OF (C) AND (D) BEING SUCH AS TO RENDER THE RATIO OF HYDROXYL GROUPS TO CARBOXYL GROUPS IN THE STARTING REACTANTS BETWEEN ABOUT 1.1 AND 2.0 TO 1, THE SAID INTERPOLYMER HAVING AN ACID VALUE BELOW
 30. 